Process of preparing compositions



Patented July 28, 1936 PATENT OFFICE PROCESS OF PREPARING COMPOSITIONSCONTAINING WOOL GREASE NAPH- THENATES Friedrich Meidert, Frankfort onthe Main- Griesheim, Germany, assignor to I. G. FarbenindustrieAktiengesellschaft, Frankfort-.on-the Main, Germany No Drawing.Application January 13,

Serial No. 651,618. In Germany July 17, 1931 Claims.

The present invention relates to a process of preparing productscontaining a combination of salts of wool grease acids and naphth-enicacid or a similar acid formed with one or several of 5 the alkalineearth metals, earth metals or heavy metals. I

I have found that new compositions can be obtained by the combination ofsalts of the wool grease acids with a salt of naphthenic acid or asimilar acid. These compositions may be used as driers for varnishes,lacquers and oil paints.

The basis of these compositions is wool grease or wool grease acidswhich may be used in the crude or purified condition. In comparison withthe hitherto. known substances containing wool grease the newcompositions hereinafter described'are of considerable advantage,particularly when they are used as driers. The advantage is derived fromthefact that the products obtained according to the present inventioncontain other acids especiallysuitable for the preparation of driers,besides wool grease or wool grease acids. As acids of this kind theremay be used, in addition to wool grease acids, the acids generally usedin the manufacture of driers, such as naphthenic acid, linoleic acid,resin acid or the acids obtainable by the oxidation of parafiin, softparaflin or petroleum. These acids, hereinused in the crudeor purifiedcondition.

As is known, wool grease can be saponified only in the presence of aconsiderable excess of alkali. According to a former'process the excessof alkali has been removed by neutralizing it with a mineral acid, avalueless waste product being produced. The neutralization by means ofsulfuric acid or hydrochloric acid entails the further drawback that,if, for instance, lead salts are 40 useisparingly soluble sulfates orchlorides are formed in the further course of the process. Largequantities of the said sulfates or chlorides are surrounded by thesticky wool grease drier and can be removed only imperfectly and by acomplicated process. All these drawbacks are avoided in the process ofthe present application. The excess of alkali required for thesaponification of wool grease is neutralized, not by. a mineral acid,but by an acid forming a valuable constituent of the drier. No valuelesswaste products are obtained, but there isproduced a mixture from alkalisoaps of the wool grease acids and the naphthenic acid or anotheradditional acid. The whole mixture can be fur ther worked up so as toproduce driers.

after called additional acids, may likewise be- According to the presentinvention the driers may be prepared by first saponifying, whileheating, wool grease or wool grease acids with an aqueous solutioncontaining an excess of caustic alkali and then neutralizing the excessof alkali by adding the equivalent quantity of one or more additionalacids. The solution of alkali soaps obtained is then caused to yield aprecipitate by adding a solution of one or more salts of an alkalineearth metal, an earth metal or a heavy metal. It is also possible to usefor the precipitation the solution of a mixture of salts containingseveral different metals. The salts of the so-called siccative metals,for instance of cobalt, manganese, lead and zinc are of particularimportance. The mixture of the salts of .wool grease acids and theadditional acids thus precipitated is then washed and the washingwater-is drawn ofi. The water which still remains in the mixture iseliminated by heating the precipitate until fusing occurs, the residualwater being thus evaporated. The fusing point is generally above 130 C.In order to accelerate the fusing process it may be advisable to carryout this process at a reduced pressure.

The stability and solubility of the products thus prepared are furtherincreased by adding to the-mixture during thecourse of the preparationaquantity of about 10 per cent. of solid monocarboxylic acids. Asmonocarboxylic acids there may be used the solid saturated fatty acids,such as stear-ic acid. Solid olefinic or aromatic carboxylic acids, thesubstitution products and derivatives thereof are likewise suitable, forinstance crotonic acid, benzoic acid, benzoyl benzoic'acid, salicylicacid, anthranilic acid, mandelic .acid, cinnamic acid or hippuric acid.

The products of the present invention may also be prepared by heatinguntil fusion occurs a mixture of wool grease or'wool grease acids andone or more additional acids together with the oxide or hydroxide of oneor more alkaline earth metals, earth metals or heavy metals or with thesalts formed by these metals with weak acids which are volatile onheating, such as acetates,'carbonates .or borates; In this case it islikewise possible to use one metal compound or simultaneously severalcompounds of different metals. The wool grease and acids applied may beused in the crude or purified condition. The fusing temperature islikewise above 130 C. In order toaccelerate the fusing process it may,in this case too, be advisable to carry out this proc- 655 at a reducedpressure.

The following examples serve to illustrate the invention, but they arenot intended to it thereto, theparts being by weight:

1.-250 parts of wool grease having an acid number of 55 and asaponification number of 125 limit are saponified, while boiling, withabout 6 times;

the quantity of caustic soda solution required (about 165 parts of NaOH)and the excess of about 145 of NaOH is neutralized with 750 parts ofnaphthenic acid having an acid number of 265. manner the neutral soapsolution is mixed, while heating it, with a solution of about 560 partsof crystallized cobalt sulfate. cobalt-wool grease-naphthenate obtainedis washed with hot water until the Glaubers salt produced during theprecipitation has been; completely eliminated. After the final washingwater has been drawn off the cobalt-wool greasenaphthenate is fused byheating it in the precipitation vessel at about 130 C. until all of thewater is eliminated. The fused mass is then directly run into thecontainers for delivery.

2.330 parts of crude or purified wool grease are saponified, while beingheated, with a caustic soda solution containing 155 parts of NaOHcorresponding to about 4 times the quantity required. The excess of NaOHamounting to'about 130 parts is neutralized with 6'70 parts ofnaphthenic acid. The soap solution obtained is diluted correspondinglyand then mixed,while being heated, first with a solution of 208 parts oflead nitrate and then with a solution of about 380 parts of crystallizedcobalt sulfate and the precipitate is washed as described in Example 1.After the final washing water has been drawn off, 4 parts of stearicacid and '4 parts-of benzoic acid are added for each 100' parts ofcobalt-lead-wool greaseenaphthenate and the whole is dehydrated, whilestirring at a temperature of about 130 C. until the watercontained inthe mixture has'completely evaporated, this being attained after a shorttime under reduced pressure.

':3.-500 parts of wool grease are saponified by boiling with causticsoda solution containing 140 fparts of NaOH, and the excess of 95 partsof NaOH is neutralizedwith 500 parts of naphthenic acid. The soapsolution is dilutedand then mixed with parts of triethanolamine; themixture is then mixed with a solution of. 40 parts of crystaliizedcobalt sulfate, 20 parts of anhydrous manganese sulfate and140'p'arts ofzinc chloride. I The precipitate is washed and dehydrated as describedin Examples 1 and 2". H

'4:-"A mixture of Z50 parts of woolgrease acids and 250 parts ofnaphthenic acid is heated to "about C.; 260 parts of litharge are thenslowly addedin small portions,'while gradually raising the temperatureto about 150 C. Stirring is continued at this temperature until'theevolution of steam has" ceased, the fused mass flows easily and 'a'dropof it placed on a glass plate'solidifies to :a "transparent solid. n

;5.' A"mixture of 500' parts of wool grease and 500 parts ofnaphthenic-acid is heated in a suit-- able vessel; Te -the mixture thereare added gradually in small portions" 300 parts of manga After havingbeen diluted in a suitable The precipitate of nese acetate, whileraising the temperature'to 200 C. to'210 C. Stirring is continued atthis temperature until the acetic acid has nearly completelydisappeared. At the same temperature 25 parts of cobaltous hydroxide areadded likewise very slowly; stirring is continued until a uniform massis obtained. The process may be finished at this stage or it may becontinued by stirring into the mass which has not been allowed to cool250 parts of linoleic acid, thus obtaininga completely homogeneous drierextract havinga very good drying power.

6.600 parts of wool grease are saponified by boiling with an aqueoussolution of 154 parts of caustic potash and the excess of 84 parts ofKOH is neutralized while the mass is hot with 400 parts of linoleicacid. The soap solution obtained is diluted with about 5 to 6 times itsweight of hot water and mixed with a solution of 290 parts of manganesesulfate (MnSOl). The precipitate thus produced is then washed 3 to 4-times at boiling temperature, thefinal washing water is drawn on and thewater still contained in the precipitate is evaporated while stirringand raising the'temperature to 130 C. to 140C. To' wards the end of thefusing process 3 parts of palmitic acid and 6 parts of crotonic acid areadded'for each 100 parts of the yield. The completely-homogeneous fusedmass is thenrun d1? rectly into the containers for delivery.

7.'400 parts of crude 'or purified'wool grease are saponified, whileboiling, by 100 parts of caustic sodasolution, about 3.3 times thequantity'required, and the excess, about 7.0 parts of NaOH, isneutralized with application of. heat by means of 600 parts of resinacid." To the neutral soap solution whichis diluted there-are firstadded at about 60f C., while stirring, a solution of about 330'parts oflead nitrate; Precipitation' is then finished with ,a solution'of aboutpartsof manganese sulfate (MnSQr). The precipitate is washed anddehydrated as de scribed in Example '1. r V

8.-300 parts 'of' wool grease orwool grease acids are saponified, whileboiling, by 1'75 parts of caustic soda solution, about 7 times the quan;

tity required, the excess of 150 parts isneutralized by adding to thehot mass first 350 parts of carboxylic acid obtainable by the'oxidationof parafiin and then' 350 parts of naphthenic acid. The soap solutionobtained is diluted,

During the dehydration 3 parts of salicylic acid and 3 parts of benzoylbenzoic acid are added for each 100 parts of the yield and the whole ismaintained at C. to" C., while stirring, until a completelyhomogeneousanhydrous' fused mass is'obtained. rThe -rfusedrmass is then run' intothe containersfor delivery and solidifies to form a brittle mass. Inthefollowing claims there is to be understood by the term sicc'ative'metals such metals as possess the property of accelerating the dryingof'the oils,

for instance the metals cobalt, manganese, lead and zinc. *L'I 1. Theprocess which comprises saponifyin'g a compound selected 'from the groupconsisting of W001 grease and woolgrease acids with an aquef oussolution containing an excess of caustic alkali, neutralizing the excessof caustic alkali with at least one acid selected from the groupgenerally used in the manufacture of driers and consisting of naphthenicacid, lino-leic acid, resin acid and the acids obtainable by theoxidation of parafiin, soft paraifin and petroleum, adding a solublesalt of at least one siccative metal washing the precipitate thusproduced with water and evaporating the Water remaining in theprecipitate by heating the precipitate to fusing.

2. The process which comprises saponifying a compound selected from thegroup consisting of wool grease and wool grease acids with an aqueoutsolution containing an excess of caustic alkali, neutralizing the excessof caustic alkali with at least one acid selected from the groupconsisting of naphthenic acid, linoleic acid, resin acid and the acidsobtainable by the oxidation of'parafiin, soft paraifin and petroleum,adding a soluble salt of a siccative metal washing the precipitate thusproduced with water, evaporating the water remaining in the precipitateby heating the precipitate to fusing, and adding a small quantity of asolid monocarboxylic acid during the course of the process.

3. The process which comprises saponifying a compound selected from thegroup consisting of wool grease and wool grease acids with an aqueoussolution containing an excess of caustic alkali, neutralizing the excessof caustic alkali with naphthenic acid, adding a soluble salt of atleast one siccative metal selected from the group consisting of cobalt,manganese, lead and zinc, washing the precipitate thus produced withwater, evaporating the water remaining in the precipitate by heating theprecipitate to fusing, the fusing process being performed at a reducedpressure and adding a small quantity of a solid monocarboxylic acidduring the course of the process.

4. The process which comprises saponifying a compound selected from thegroup consisting of wool grease and wool grease acids with an aqueoussolution containing an excess of caustic alkali, neutralizing the excessof caustic alkali with naphthenic acid, adding a soluble cobalt salt anda soluble manganese salt, washing the pre oipitate thus produced withwater and evaporating the water remaining in the precipitate by heatingthe precipitate to fusing.

5. The process which comprises saponifying a compound selected from thegroup consisting of wool grease and wool grease acids with an aqueoussolution containing an excess of caustic alkali, neutralizing the excessof caustic alkali with naphthenic acid, adding a soluble lead salt and asoluble manganese salt, washing the precipitate thus produced with waterand evaporating the water remaining in the precipitate by heating theprecipitate to fusing.

FRIEDRICH MEIDERT.

